IE863126L - Thioxanthones, photoinitiators - Google Patents
Thioxanthones, photoinitiatorsInfo
- Publication number
- IE863126L IE863126L IE863126A IE312686A IE863126L IE 863126 L IE863126 L IE 863126L IE 863126 A IE863126 A IE 863126A IE 312686 A IE312686 A IE 312686A IE 863126 L IE863126 L IE 863126L
- Authority
- IE
- Ireland
- Prior art keywords
- formula
- group
- derivative
- thioxanthone
- hereinbefore described
- Prior art date
Links
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007650 screen-printing Methods 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 241001508691 Martes zibellina Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000010992 reflux Methods 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- -1 sulphuric acid ester Chemical class 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SYZJDGAOLGLIDX-UHFFFAOYSA-N 1-hydroxyazocane Chemical compound ON1CCCCCCC1 SYZJDGAOLGLIDX-UHFFFAOYSA-N 0.000 description 3
- URCLHZFMMKQMDR-UHFFFAOYSA-N 2-hydroxy-3,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(O)=C(C)C(C)=C3SC2=C1 URCLHZFMMKQMDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OEZKDMYTQDZSAZ-UHFFFAOYSA-N 1-hydroxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O OEZKDMYTQDZSAZ-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012258 stirred mixture Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- LHXGLTZNCXCSKG-UHFFFAOYSA-N 2-hydroxy-4-methylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C)=CC(O)=C2 LHXGLTZNCXCSKG-UHFFFAOYSA-N 0.000 description 1
- ANHLDZMOXDYFMQ-UHFFFAOYSA-N 2-hydroxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(O)=CC=C3SC2=C1 ANHLDZMOXDYFMQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DFODRYKLSOESHG-UHFFFAOYSA-N C1=CC=C2C(=C1)C(=O)C3=C(O2)C=CC(S3)O Chemical class C1=CC=C2C(=C1)C(=O)C3=C(O2)C=CC(S3)O DFODRYKLSOESHG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- BKAYIFDRRZZKNF-VIFPVBQESA-N N-acetylcarnosine Chemical compound CC(=O)NCCC(=O)N[C@H](C(O)=O)CC1=CN=CN1 BKAYIFDRRZZKNF-VIFPVBQESA-N 0.000 description 1
- FPTYJMPFIFFGDY-UHFFFAOYSA-N OC1=CC=CC2=C1SC1=CC=CC=C1C2=O.Cl Chemical compound OC1=CC=CC2=C1SC1=CC=CC=C1C2=O.Cl FPTYJMPFIFFGDY-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BHSXDBHWCVQBIE-UHFFFAOYSA-M [2-hydroxy-3-(4-methyl-9-oxothioxanthen-2-yl)oxypropyl]-trimethylazanium;chloride Chemical compound [Cl-].S1C2=CC=CC=C2C(=O)C2=C1C(C)=CC(OCC(O)C[N+](C)(C)C)=C2 BHSXDBHWCVQBIE-UHFFFAOYSA-M 0.000 description 1
- WBGVJHCTOFQFSR-UHFFFAOYSA-M [2-hydroxy-3-(9-oxothioxanthen-4-yl)oxypropyl]-trimethylazanium;chloride Chemical compound [Cl-].S1C2=CC=CC=C2C(=O)C2=C1C(OCC(O)C[N+](C)(C)C)=CC=C2 WBGVJHCTOFQFSR-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005236 alkanoylamino group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/12—Production of screen printing forms or similar printing forms, e.g. stencils
Abstract
The invention provides thioxanthone derivatives of general formula <IMAGE> (I) wherein one of R2, R3 and R4 is a group of formula <IMAGE> (II) in which one of R5, R6 and R7 is an alkyl or a benzyl group, the others being alkyl groups and A- represents an anion, and R1 and the others of R2, R3, and R4 are independently selected from hydrogen atoms, alkyl groups and alkoxy groups; and the use of such derivatives as photoinitiators, particularly in aqueous photopolymerizable compositions for the production of stencils for screen printing.
[US4791213A]
Description
9500 2 This invention relates to thioxanthone derivatives, their preparation, photopolymerisable compositions containing them, use of such compositions in the production of stencils for screen printing, screens for screen printing coated with such compositions, and the use of thioxanthone derivatives as photoinitiators.
Three main photosensitive systerrs are used in screen printing, which are usually referred to as direct, indirect and direct/indirect methods. The prior art photoinitiators include certain dichranate ccrrpounds, polymeric diazonium salts and a leuco sulphuric acid ester of an indigo or thioindigo dye. When these photoinitiators are employed in any of the screen printing methods they suffer the disadvantage of being sparingly soluble in water so necessitating the addition of a solution of a peroxide or employment of large quantities of hxmectant or use of two pack systems.
In order to overcome these difficulties, EP-A-81280 discloses that certain thioxanthones containing anionic groups such as car boxylie acid or sulphonic acid groups, have useful solubility in water of a suitable pH and can be used as photoinitiators in screen printing. These thioxanthones have the formula 3 10 15 (OR ) -A m where R is halogen, alkyl, alkoxy, alkylthio, nitro, amino, alkylamino, dialkylamino, hydroxyaIkylamino, alkanoylamino, benzoylamino, N-alkanoyl-N-benzoylamino, sulphonamido or acetyl, 2 R is alkylene of 1 to 4 carbon atcrns, n is 0, 1 or 2, m is 1 or 2, and A is -C00H, -S03Hf -0603H, or -OCO-X-OOOH (where X is such that HOOC-X-COOH is a di- or tri- carboxylic acid of up to 8 carbon atcms), the aforesaid alkyl, alkoxy, and alkenyl residues containing up to 4 carbon atcms each, and water-soluble salts thereof.
There have now been discovered certain novel thioxanthone derivatives which are very water-soluble over a wide pH range.
According to the present invention there are provided thioxanthone derivatives of general formula (I) 20 2 3 4 wherein one of R , R and R is a group of formula R5 '+ 6 - 0 - CH_ - CH - CH-, - N - R . I 2 | 2 OH (in in which one of R"*, R^ and R^ is an alkyl or a benzyl group, the others being alkyl groups and A represents an anion, and R* and 2 3 4 the others of R , R , and R are independently selected frcri hydrogen a tans, alkyl groups and alkoxy groups. 12 3 4 An alkyl or alkoxy group R , R , R or R is preferably a C^_g alkyl or alkoxy group, more preferably a alkyl or C. . alkoxy (e.g. methoxy) group. In preferred embodiments of 1 2 3 4 the invention, R and said others of R , R and R are independently selected frcm hydrogen atcms and methyl groups.
It is preferred for one of R^, R^ and R7 to be a alkyl group (e.g. a cetyl group) or a benzyl group, the others being alkyl, preferably alkyl, groups. In preferred embodiments of the invention, R^, R^ and R7 are all methyl groups. - 2- A may represent h of a divalent anion, e.g. JjSO^ , but is preferably a monovalent anion e.g. a halide ion. A preferably represents a chlorine or brcmine atan, and is very conveniently a chlorine atan. 2 4 Thioxanthone derivatives of formula I wherein R or R represents the group cf formula II are preferred.
The invention further provides a process for the preparation of a thioxanthone derivative of formula I as defined above which comprises reacting a hydroxythioxanthone corresponding to formula I wherein in place of the group of formula II is a hydroxy group, with a catpound of formula R5 '+6 CH- - CH - CH_ - N - R . A (III) i9 k* 2 R7 5 6 7 —. wherein R , R , R and A are all as defined for the group of 8 9 8 formula II, R is a group -OH and R is a leaving group, or R g and R together represent an oxygen atan, in the presence of a base. g A leaving group R may conveniently be a halogen atan. 8 9 Preferably when R is a group -OH, R is a chlorine atan.
The hydroxythiaxanthones corresponding to formula I wherein in place of the group of formula II is a hydroxy group are either known ccnpounds, preparable by kncwn methods, or they may be prepared by methods analogous to kncwn processes. Suitable methods will be apparent to those skilled in the art by 5 reference to, for example, EP-A-81280; DE-A-2504642; Czechoslovakian Patent No. 145,016; R.N. Sen and S.C. Sen Gupta, J. Ind. Chan. Soc., 1929, £, 273; H. Christopher and S. Smiles, J.C.S., 1911, 99, 2050-1; and A. Mustafa and O.H. Hishnat, 5 J.A.C.S., 1957, 79, 2227-8.
Reaction of the hydroxythioxanthone with the compound of fonnala III may conveniently be effected using an alkanol e.g. a C^_2 alkanol, conveniently ethanol, or a polar aprotic solvent such as N,N-dimethy 1 formairiide as solvent, at temperatures in the 10 range 60°C to reflux tanperature. Reaction at reflux tenperature is very convenient. Convenient bases include alkali metal (e.g. sodium or potassinn) alkoxides and hydroxides.
Further in accordance with the invention there is provided an aqueous photqpolymerisable conposition comprising an aqueous 15 dispersion or solution of at least one polymerisable monomer and, as photoinitiator, a thioxanthone derivative of formula I. The invention also extends to the use of such a composition in the production cf a stencil for screen printing, and to screens for screen printing coated with such a composition and dried. 20 Suitable such aqueous photcpolymerisable compositions comprise corpositions as described in EP-A-81280, substituting a thioxanthone derivative of formula I for the photoinitiator thioxanthone thereof. Accordingly the disclosure of EP-A-81280 is incorporated herein by reference. 25 The invention also comprises the use of a derivative of formula I as photoinitiator.
Compounds of formula I possess the property of having useful absorption of actinic light above 330nm. In addition to their use a photoinitiators as described above in 30 photopolymerisable corpositions, they may also be employed in the manufacture of water based U.V. curable inks.
The invention will be further understood from the following Exairples, of which Examples 1 to 6 relate to the preparation of compounds of formula I, and Example 7 demonstrates efficacy of 35 the compounds as photoinitiators.
Example 1 2-Hydroxy-3- (9-oxo-9H-thioxanthen-4-yloxy) -N,N,N-trimethyl-prcpanaminium chloride 4-Hydroxythioxanthone (5.7g) (mp 284.5 to 286.5°C, prepared 5 by methods analogous to those of DE-A-2 504 642 and Czechoslovakian Patent No. 145,016) and glycidyl trine thylamnonium chloride (5.44g, 70% assay) together with absolute ethanol (95ml) were stirred and brought to reflux whereupon the pH was adjusted to ca. 9 by the addition of a few 10 drops of ethanolic sodium ethoxide solution (3% w/v). After four minutes refluxing a clear solution resulted and after a further three hours refluxing a crystalline solid appeared.
After refluxing for a further three and one half hours, water (7mls) was added and the pH was adjusted to ca. 3 by the 15 addition of a few drops of 2N isopropanolic hydrogen chloride. Hot filtration followed by ice bath cooling of the filtrate and filtration gave the crude title compound which was washed with isopropanol and dried in an air oven at 60°C. The dull pale green solid (8.58g; mp 267 to 268°C) was recrystallised from a 20 mixture of ethanol (90mls) and water (7mls), washed with ethanol and dried, giving 2-hydroxy-3- (9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-l-propanaminium chloride (7.03g; 87.8%) as light green crystals, np 268.5-269.2°C.
Analysis: 25 Calc. for C19H22C1NC3S: 0.25H20; C 59.36; H 5.90, N 3.64; CI 9.22; S 8.34 Found: C 59.53; H 5.76; N 3.63; CI 9.48; £ 8.40.
An aqueous solution of this compound has an absorption maximum at 391nm with an E (1%; 1cm) of 149. 30 Example 2 2-Hydroxy-3- (l-methyl-9-oxo-9H-thioxar.then-4-yloxy) -N,N,N-trimethyl-l-propanaminium chloride 4-Hydroxy- 1-methy 1 thioxanthone (6.05g), (prepared by a method analogous to that of R.N. Sen and S.C. Sen Gupta, J. Ind. 35 Chem. Soc., 1929, 6_, 2730) and glycidyl trimethylanmonium 7 chloride (5.44g; 70% assay) together with absolute alcohol (60mls) were stirred and brought to reflux whereupon the pH was adjusted to ca. 9 by the addition of a few drops of ethanolic sodiurr ethoxide solution (3% w/v). After two minutes refluxing 5 a clear solution resulted and after a further two hours refluxing a crystalline solid appeared. This was redissolved by the addition of water (13mls) and refluxing continued for an additional four hours. After adjusting the pH to ca. 4 by the addition of a few drops of 2N iscprqpanolic hydrogen chloride 10 hot filtration followed by ice bath cooling of the filtrate and filtration gave the crude title compound which was washed with ethanol and vacuum dried.
The yellow solid (6.37g; mp 269 to 270.5°C) was recrystallised frar. ethanol containing a little water, washed 15 with ethanol and dried in an air oven at 70°C giving 2-hydroxy-3- (l-methyl-9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-triirethyl-l-propanairiinium chloride (4.5g; 45.6%) as yellow crystals (irp 271 to 272°C).
Analysis: 20 Calc. for C2()H24C1N03S: C 60.98; H 6.14; N 3.56; CI 9.00; S 8.14 Found : C 60.70; H 6.15; N 3.48; CI 9.01; S 8.13 Ar. aqueous solution of this compound has an absorption maximum 25 at 39Crar. with an E (1%; lan) of 134.5.
Example 3 2-Hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -K,N,N-trijnethyl-l-propanaminium chloride Sodium (1.36g) was reacted with absolute ethanol (12Qmls) 30 and 2-hydroxy-thioxanthone (11.4g) (prepared by a method analogous to that of H. Christopher and S. Sniles, J.C.S., 1911, 99, 2050-2051) was added. To the stirred refluxing mixture (3-chloro-2-hydroxypropyl)trimethyl aimonium chloride (10.7g) was added and the mixture refluxed overnight. After adjusting 35 the pH to ca. 4 via the addition of a few drops of 2N » J 8 isopropanolic hydrogen chloride solution, hot filtration followed by ice bath cooling of the filtrate and filtration gave the crude title compound which was washed with methanol and vacuum dried. 5 The yellcv? sclid (15.3g; np 245 to 246.5°C) vras recrystallised frcm a mixture of ethanol (150mls) and methanol (40mls), washed with ethanol and vacuum dried giving 2-hydroxy-3- (9 -oxo- 9H-thioxanthen-2-y loxy) -N,N',N-trimethyl-l-propanaminium chloride (14.5g; 72.8%) as yellow crystals, np 245 10 to 246.5°C.
Analysis: Calc. for c19H22C1NT03S: IHjO: C 57.35; H 6.08; N 3.52; CI 8.91; S 8.06.
Found : C 57.73; H 6.01; N 3.40; CI 8.77; S 8.02. 15 An aqueous solution of this compound has an absorption maximum at 404nm with an E (1%, Ian) of 135.
Example 4 2-Hydroxy-3- (4 -me thy l-9-oxo-9H-thioxanthen- 2-y loxy) -N,N,N-trimethyl-l-propanarainium chloride 20 2-Hydroxy-4-methylthioxanthone (6.5g) (prepared by a method analogous to that of A. Mustafa and O.H. Hishmat, J.A.C.S., 1957, 79, 2227-8) and glycidyl trimethylanmoniurr. chloride (5.12g; 80% assay) together with absolute alcohol (70mls) were stirred and brought to reflux, whereupon the pH was adjusted to 25 ca. 9 by the addition of a few drops of ethanolic sodium ethoxide solution (3%w/v). After two hours refluxing a clear solution resulted and after a further 18 hours reflux a crystalline solid appeared. Solution was effected by the addition of methanol (70mls) followed by water (2mls) and the 30 mixture was re fluxed overnight. After adjusting the pH to ca. 4 by the addition of a few drops of 2N isopropanolic hydrogen chloride, hot filtration fcllcwed by ice bath cooling of the filtrate and subsequent filtration gave the crude title ocnipound which was washed twice with ethanol and vacuum dried. 35 The yellow solid (9.6g; np 247 to 253°C) was recrystallised 9 frcm a mixture of ethanol (60mls), methanol (60mls) and water (6mls), washed with ethanol and vacuun dried giving 2-hydroxy-3-(4-methyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-l-propanaminium chloride (8.0g; 77.7%) as yellow 5 crystals, mp 253.3 to 255°C.
Analysis: Calc. C20H24C1U03S: 1H20: C 58.33; H 6.36; N 3.40; CI 8.61; S 7.78.
Found C 58.65; H 6.54; N 3.27; CI 8.51; S 7.73. 10 An aqueous solution of this ccrnpound has an absorption maximum at 404nm with an E (1%; Ian) of 144.
Example 5 2-Hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-ylGxy) -N,Katrine thy 1-1-propanairunium chloride 15 2-Hydroxy-3,4-dimethylthioxanthone (np 309-310°C after recrystallisation frar. 70% v/v dimethylformamide/water; microanalysis:- Calcd. for ci5Hi2°2S: C ^0,^0; H 4.72; S 12.51. Found C 70.22; H 4.73; S 12.37) was prepared by adding 2,3-dinethylphenol (24.4g) during two hours to a stirred mixture 20 of 2,2'-dithiobisbenzoic acid (15.3g) and canc. sulphuric acid (15Qmls) whilst the temperature was kept at 15 ± 5°C via ice bath cooling. The temperature was then raised to 65°C and maintained at 65 + 5°C for one hours after which the mixture was allowed to cool for 16 hours, before being quenched into water 25 (500rrls) at 95 ± 5°C and then stirred for thirty minutes prior to filtration. The residue was washed twice with water and then slurried in water (250 mis) at 70°C and sodiun bicarbonate (44g) was slcwly added until the pH became 8. After boiling for ten minutes the mixture was filtered and the residue washed 30 sequentially with water (X3) then isopropanol (XI). Drying in an air oven at 60°C gave crude 2-hydroxy-3,4-dimethylthioxanthone (18.59g) as dull yellcw crystalline solid, np 298 to 302°C. 2-Hydroxy-3,4-dimethylthioxanthone (6.4g) was dissolved in 35 dimethyl formamide (40mls) at 104 °C and after hot filtration, 1 o glycidyl trime thy lannionium chloride (5.44g; 70% assay) as a slurry in dimethylformarrdde (lOmls) was added to the filtrate at 1006C. The pH v©s adjusted to ca.9 by the addition of a few drops of ethanolic sodium hydroxide solution (3% w/v) and after 5 twelve minutes stirring at 100"c a crystalline solid appeared. After a further six hours stirring at 100°C the pH was adjusted to ca.6 by the addition of a few drops of 2N isopropanolic hydrogen chloride and then the mixture was cooled in an ice bath. Filtration followed by sequential washing of the residue 10 with dimethyl formamide (XI) and isoprqpanol (X3) and then air drying at 70°C gave 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thicKanthen-2-y loxy) -N ,N ,N-trimethyl-l-propanaminiurn chloride (7.57g; 72.4%) as a pale yellow solid, np 271.5 to 273.5°C. Analysis: 15 Calc. for C^H^ClNCy 0.75 H20.
C 59.82; H €.58; N 3.36; CI 8.41; S 7.61. Found C 59.90; H 6.55; N 3.23; CI 8.53; S 7.69.
An aqueous solution of this compound has an absorption maximum at 402nm with an E (1%; lan) of 115. 20 Example 6 2-Hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthsn-2- ylox-y) -N, N, N-trimethyl- 1-propanaminium chloride 2-Hydroxy-l,3,4-txiinethylthiaxanthone was prepared by adding 2,3,6-trimethylphenol (18.6g) during two hours to a 25 stirred mixture of 2,2'-dithiobisbenzoic acid (30.6g) and conc. sulphuric acid (300rrls) whilst the temperature was kept at 12.5 t 2.5°C via ice bath cooling. After heating at 75 i 5°C for one hour the mixture was cooled to 50 °C prior to stirring into hot water (2 litres). Filtration, followed by water 30 washing and drying in an air oven at 70 °C gave the crude product which was recrystallised from a mixture of dimethylfonramide (140mls) and water (60mls). Filtration followed by washing (H20) and drying at 70°C gave 2-hydroxy-l,3,4-trimethyl-thioxanthone (38.4g; 71.1%) as khaki crystals, np 201 to 204CC. 35 2-Hydroxy-l,3,4-trimethylthioxanthone (6.75g) and glycidyl- 1 i trime thy lairnonium chloride (6.44; 70% assay) together with absolute alcohol (6Qrrls) were stirred and brought to reflux whereupon the pH was adjusted to ca. 9 via the addition of a few drops of ethanolic sodium ethoxide solution (3% w/v). After 5 refluxing for one hour a clear solution resulted. The mixture was re fluxed for 16 hours and methanol OOmls) plus water (2mls) were added to effect honogenity. After adjusting the pH to ca.3 by the addition of a few drops of 2N isopropanolic hydrogen chloride solution hot filtration followed by ice bath cooling of 10 the filtrate and subsequent filtration gave the crude title carpound which was washed thrice with ethanol and vacuum dried. The fawn solid (9.21g; np 258.5 to 260.5°C) was recrystallised from a mixture of ethanol (75mls) and methanol (9Qmls), washed with ethanol and vacuum dried giving 2-hydroxy-3-(1,3,4-15 trime thy l-9-oxo-9H-thioxanthen-2-y loxy) -K,N,N-trimethyl- propanaminium chloride (6.5g, 61.0%) as fawn crystals, np 264.5 to 265.5°C.
Analysis: Calc. for C22H2gClH03S: 0.25H20: 20 C 61.94; H 6.74; N 3.28; CI 8.30; S 7.52.
Found: C 62.26; H 6.76; N 3.23; CI 8.17; S 7.42.
An aqueous solution of this carpound has an absorption neximum at 390rm with an E (1%; lan) of 111.
Example 7 25 Evaluation of the Efficiency of the Ccnpounds given in Exarrples 1 tc 6 as Water Soluble Photoinitiators Each of the conpounds described in the previous examples was investigated as follows. A sample (0.33g) was dissolved in water (0.8mls) and K,N-dimethylarninoethanol (0.7icJLs) added. 30 This solution was stirred into "Azocol S" (Trade Mark) emulsion (30g) and then N,N'-methylenebisacrylainide (lg) added. After stirring for five minutes the mixture was allowed to stand for 16 hours prior to coating into orange polyester screen (110 threads/an) with two coats on the direct side and one on the 35 reverse. The coated screen was air dried and then irradiated by 12 light which had passed first through a piece of plate glass (5mn thick) and second through a film containing a positive image. The screen, film and glass in the form of a tight sandwich sat directly below two 375 watt photographic lanps whose bottom 5 surfaces were positioned at a distance of 35 cms from the top surface of the piece of glass. After irradiating for a given time period the screens were gently rinsed with running cold water until an image began to form and then such treatment continued for a further two minutes. The screens vere then air 10 dried and the stencils examined. Ey using stepwise increasing exposure times the ndnimum time needed to give a good quality stencil was determined and these times are reproduced in the table below. For comparison a standard sensitized "Azocol S" emulsion was prepared according to the manufacturers 15 instructions and after processing as described above its minimum exposure time was determined. Also the sodium salt of 2-(3-sulphoprqpoxy)- thioxanthone (Example 2 of EP-A-81280) was tested as above (comparative A) for comparison purposes.
Results 20 Carpound of Example No. Exposure Time in Seconds 1 4 2 2 3 8 4 2 25 5 4 6 8 Standard Compound 30 Comparative A 8 These results prove the efficiency of the compounds of the 30 present invention as water soluble photoinitiators.
"Azocol S" emulsion is a partially hydrolysed polyvinyl acetate emulsion in water. The recoraiended photosensitiser provided is a diazonium salt of paraphenylene diamine/formaldehyde cross-linked polymer. »
Claims (15)
1. A thioxanthone derivative of general fomula (I) 2 3 4 wherein one of R , F and R is a group of formula R5 - 0 - CH_ - CH - CH- - - R6 . A~ (II) 2 I 2 17 OH R in which one of R^, R^ and R7 is an alkyl or a benzyl group, the others being alkyl groups and A~ represents an 1 2 3 4 anion, and R and the others of R , R , and R are independently selected from hydrogen atoms, alkyl groups and alkoxy groups.
2. A derivative according to Claim 1 wherein R* and said 2 3 4 others of R , R and R are independently selected from hydrogen atoms and methyl groups.
3. A derivative according to Claim 1 or 2 wherein R^, R^ and 7 R are all methyl groups.
4. A derivative according to Claim 1, 2 or 3 wherein A represents a chlorine or brardne atan. 2
5. A derivative according to any of Claims 1 to 4 wherein R 4 or R represents the group of formula II.
6. A process for the preparation of a thioxanthone derivative of formula I as defined in any of Claims 1 to 5 which carprises reacting a hydroxythioxanthcne corresponding to formula I wherein in place of the group of formula II is a hydroxy group, with a carpound of formula R5 I J £ - CK_ - CH - CH_ - K - R . A (III) R8 R7 wherein R", R^, R7 and A~ are all as defined for the group 8 9 of formula II, R is a group -OH and R is a leaving group, 8 9 or P and R together represent an oxygen atan, in the presence of a base. g
7. A process according to Claim 6 wherein when R is a group 9 -OH, R is a chlorine atan.
8. An aqueous photopolymeri sable ccrposition catprising an aqueous dispersion or solution of at least one polymerisable monomer and, as photoinitiator, a thioxanthone derivative of formula I according to any of Claims 1 to 5.
9. The use of a ccrposition according to Claim 8 in the production of a stencil for screen printing.
10. A screen for screen printing coated with a composition according to Claim 8 and dried. 1 5
11. A derivative according to Claim 1, substantially as hereinbefore described with particular reference to Examples 1-6 of the accompanying Examples.
12. A process for the preparation of a derivative 5 according to Claim 1, substantially as hereinbefore described with particular reference to Examples 1-6 of the accompanying Examples.
13. A derivative according to Claim 1, whenever prepared by a process claimed in a preceding claim. 10
14. An aqueous photopolymerisable composition according to Claim 8, substantially as hereinbefore described with particular reference to Example 7 of the accompanying Examples.
15. A screen according to Claim 10, substantially as 15 hereinbefore described with particular reference to f Example 7 of the accompanying Examples. F.R. KELLY & CO. AGENTS FOR THE APPLICANT.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB858529448A GB8529448D0 (en) | 1985-11-29 | 1985-11-29 | Thioxanthone derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE863126L true IE863126L (en) | 1987-05-29 |
| IE59500B1 IE59500B1 (en) | 1994-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE312686A IE59500B1 (en) | 1985-11-29 | 1986-11-27 | Thioxanthone derivatives |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4791213A (en) |
| EP (1) | EP0224967B1 (en) |
| JP (1) | JPH0788377B2 (en) |
| CN (1) | CN1020454C (en) |
| AU (1) | AU586051B2 (en) |
| BR (1) | BR8605813A (en) |
| CA (1) | CA1277328C (en) |
| DE (1) | DE3664469D1 (en) |
| DK (1) | DK164320C (en) |
| EG (1) | EG18427A (en) |
| ES (1) | ES2009785B3 (en) |
| GB (1) | GB8529448D0 (en) |
| GR (1) | GR3000160T3 (en) |
| HU (1) | HU205104B (en) |
| IE (1) | IE59500B1 (en) |
| IL (1) | IL80800A0 (en) |
| NZ (1) | NZ218425A (en) |
| PT (1) | PT83820B (en) |
| ZA (1) | ZA868979B (en) |
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| DE3677527D1 (en) * | 1985-11-20 | 1991-03-21 | Mead Corp | IONIC COLORS AS PHOTOSENSITIVE MATERIALS CONTAINING INITIATORS. |
| DE3606155A1 (en) * | 1986-02-26 | 1987-08-27 | Basf Ag | PHOTOPOLYMERIZABLE MIXTURE, THIS CONTAINING LIGHT-SENSITIVE RECORDING ELEMENT, AND METHOD FOR PRODUCING A FLAT PRINT MOLD BY THIS LIGHT-SENSITIVE RECORDING ELEMENT |
| US5262276A (en) * | 1988-05-11 | 1993-11-16 | Fuji Photo Film Co., Ltd. | Light-sensitive compositions |
| US5047568A (en) * | 1988-11-18 | 1991-09-10 | International Business Machines Corporation | Sulfonium salts and use and preparation thereof |
| IL111014A (en) * | 1994-09-21 | 1999-05-09 | Scitex Corp Ltd | Ink compositions and a method for making same |
| US5714360A (en) * | 1995-11-03 | 1998-02-03 | Bsi Corporation | Photoactivatable water soluble cross-linking agents containing an onium group |
| TW466256B (en) | 1995-11-24 | 2001-12-01 | Ciba Sc Holding Ag | Borate photoinitiator compounds and compositions comprising the same |
| DE69704969T2 (en) * | 1996-02-20 | 2002-04-04 | Asahi Chemical Ind | Process for the production of a photosensitive plastic printing plate |
| US6025408A (en) * | 1997-03-27 | 2000-02-15 | First Chemical Corporation | Liquid thioxanthone photoinitiators |
| FR2872409B1 (en) * | 2004-06-30 | 2007-02-09 | Rhodia Chimie Sa | PHOTOPOLYMERIZABLE DENTAL COMPOSITION |
| US20050261390A1 (en) * | 2004-05-13 | 2005-11-24 | Jean-Marc Frances | Stable cationically crosslinkable/polymerizable dental composition with a high filler content |
| US7893130B2 (en) * | 2004-05-13 | 2011-02-22 | Bluestar Silicones France Sas | Photocurable dental composition |
| WO2005120439A1 (en) * | 2004-05-13 | 2005-12-22 | Rhodia Chimie | Photopolymerisable dental composition |
| US20060150847A1 (en) * | 2004-10-12 | 2006-07-13 | Presstek, Inc. | Inkjet-imageable lithographic printing members and methods of preparing and imaging them |
| WO2007032818A2 (en) | 2005-09-12 | 2007-03-22 | Zoltan Laboratories Llc | Compounds and compositions to control abnormal cell growth |
| US20070154518A1 (en) * | 2005-12-29 | 2007-07-05 | Robert Falotico | Photoactive biocompatible coating composition |
| US20080114055A1 (en) * | 2006-11-10 | 2008-05-15 | Zoltan Laboratories Llc | Thioxanthone Compounds to Reverse Weight Loss |
| US20080207738A1 (en) * | 2007-02-28 | 2008-08-28 | Cancure Laboratories, Llc | Drug combinations to treat drug resistant tumors |
| JP5148235B2 (en) * | 2007-09-28 | 2013-02-20 | 富士フイルム株式会社 | Ink composition |
| FR3067030B1 (en) * | 2017-06-02 | 2019-07-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | DEVICE AND METHOD FOR PRODUCING AN OBJECT |
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|---|---|---|---|---|
| GB1434486A (en) * | 1974-02-04 | 1976-05-05 | Ici Ltd | Thioxanthene derivatives |
| CH640849A5 (en) * | 1979-05-18 | 1984-01-31 | Ciba Geigy Ag | THIOXANTHONICARBONIC ACID ESTERS, THIOESTERS AND AMIDES. |
| US4418138A (en) * | 1981-11-03 | 1983-11-29 | Sericol Group Limited | Photopolymerizable materials for use in producing stencils for screen printing |
| GB2108487B (en) * | 1981-11-03 | 1985-07-31 | Sericol Group Ltd | Water soluble thioxanthone photoinitiators |
| US4602097A (en) * | 1984-06-11 | 1986-07-22 | Ulano Corporation | Water soluble photoinitiator benzophenone and thioxanthenone ethoxy-ether derivatives |
-
1985
- 1985-11-29 GB GB858529448A patent/GB8529448D0/en active Pending
-
1986
- 1986-11-05 US US06/927,018 patent/US4791213A/en not_active Expired - Fee Related
- 1986-11-06 CA CA000522382A patent/CA1277328C/en not_active Expired - Fee Related
- 1986-11-26 CN CN86107935A patent/CN1020454C/en not_active Expired - Fee Related
- 1986-11-26 EG EG737/86A patent/EG18427A/en active
- 1986-11-27 DK DK572186A patent/DK164320C/en not_active IP Right Cessation
- 1986-11-27 HU HU864918A patent/HU205104B/en not_active IP Right Cessation
- 1986-11-27 ZA ZA868979A patent/ZA868979B/en unknown
- 1986-11-27 DE DE8686202118T patent/DE3664469D1/en not_active Expired
- 1986-11-27 IL IL80800A patent/IL80800A0/en not_active IP Right Cessation
- 1986-11-27 JP JP61280932A patent/JPH0788377B2/en not_active Expired - Lifetime
- 1986-11-27 BR BR8605813A patent/BR8605813A/en unknown
- 1986-11-27 PT PT83820A patent/PT83820B/en not_active IP Right Cessation
- 1986-11-27 AU AU65751/86A patent/AU586051B2/en not_active Ceased
- 1986-11-27 ES ES86202118T patent/ES2009785B3/en not_active Expired
- 1986-11-27 EP EP86202118A patent/EP0224967B1/en not_active Expired
- 1986-11-27 IE IE312686A patent/IE59500B1/en not_active IP Right Cessation
- 1986-11-27 NZ NZ218425A patent/NZ218425A/en unknown
-
1989
- 1989-09-20 GR GR89400177T patent/GR3000160T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EG18427A (en) | 1993-02-28 |
| PT83820A (en) | 1986-12-01 |
| US4791213A (en) | 1988-12-13 |
| DK572186D0 (en) | 1986-11-27 |
| GB8529448D0 (en) | 1986-01-08 |
| EP0224967A1 (en) | 1987-06-10 |
| CA1277328C (en) | 1990-12-04 |
| BR8605813A (en) | 1987-08-25 |
| JPS62132880A (en) | 1987-06-16 |
| DK164320C (en) | 1992-11-02 |
| HUT44025A (en) | 1988-01-28 |
| DK572186A (en) | 1987-05-30 |
| DK164320B (en) | 1992-06-09 |
| AU6575186A (en) | 1987-06-04 |
| PT83820B (en) | 1988-10-14 |
| ES2009785B3 (en) | 1989-10-16 |
| CN86107935A (en) | 1987-07-08 |
| ZA868979B (en) | 1987-07-29 |
| NZ218425A (en) | 1988-10-28 |
| IL80800A0 (en) | 1987-02-27 |
| DE3664469D1 (en) | 1989-08-24 |
| GR3000160T3 (en) | 1990-12-31 |
| EP0224967B1 (en) | 1989-07-19 |
| IE59500B1 (en) | 1994-03-09 |
| CN1020454C (en) | 1993-05-05 |
| AU586051B2 (en) | 1989-06-29 |
| JPH0788377B2 (en) | 1995-09-27 |
| HU205104B (en) | 1992-03-30 |
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| MM4A | Patent lapsed |